Cross, Warren Bradley; (2003) Chemical vapour deposition of tungsten oxide thin films from single-source precursors. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

This thesis describes the chemical vapour deposition (CVD) of tungsten oxide thin films on glass from a wide range of single-source precursors. Chapter 1 describes previous work that has motivated this research. Chapter 2 discusses the synthesis of conventional style candidates for single-source precursors. Reactions of WOCl4 with 3-methyl salicylic acid (MesaliH2) and 3,5-di-iso-propyl salicylic acid (di-i-PrsaliH2) yielded the ditungsten complexes [WO(Mesali)(MesaliH)2(μ-O)], 1, and [WO(di-i-Prsali)(di-i-PrsaliH)2(μ-O)], 2, and the monotungsten complex [WO(di-i-Pr sali)(di-i-PrsaliH)Cl], 3. Tungsten(VI) dioxo complexes were prepared by ligand exchange reactions of [WO2(acac)2], 4, yielding [WO2(catH)2], 5, and [WO2(malt)2], 6, (catH2 = 3,5-di-tert-butyl-catechol; maltH = maltol). Chapter 3 describes thermal analyses of the complexes 1 - 6 and tungsten hexaphenoxide, and consequently their suitability for CVD. The use of [W(OPh)6] and 2 - 6 in aerosol assisted CVD is reported in Chapter 4. Brown tungsten oxide was deposited from 2 and 3 at 600 °C; blue partially-reduced WO3-x thin films were deposited from [W(OPh)6] from 300 to 500 °C, from 4 at 600 °C and 6 at 620 °C. Sintering all of the coatings in air at 550 °C afforded yellow films of stoichiometric WO3. Raman spectroscopy and glancing angle XRD showed that coatings deposited from [W(OPh)6] at 300 °C were amorphous, whereas all the other films were the monoclinic phase γ-tungsten oxide. Taking full advantage of the aerosol vaporisation technique led to the CVD of tungsten oxide films from polyoxometalate single-source precursors, as described in Chapter 5. The isopolyanion [nBu4N]2[W6O19], 7, afforded WO3 at 410 °C; the heteropolyanions [nBu4N]4H3[PW11O39], 8, and [nBu4N]4[PNbW11O40], 9, were used to deposit doped WO3 thin films in a highly-controlled manner at 480 °C. Thus, the unprecedented use of large, charged clusters for CVD was demonstrated. Chapter 6 describes investigations of the tungsten oxide films as photocatalysts for the destruction of organic pollutants. Fully-oxidised, yellow WO3 coatings showed excellent photocatalytic activity for the destruction of an over-layer of stearic acid. This could lead to the application of tungsten oxide films on glass as self-cleaning windows.

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